Carboxylic acid amido-alkyl-amino ester salts



Patented Aug. 17, 1954 UNITED STATES PATENT OFFICE CARBOXYLIC ACID AMIDO-ALKYL-AMINO ESTER SALTS Lane, Eccles, Manchester, England, a corpora- Claims priority, application Great Britain November 20, 1950 i 13 Claims. (CI. 260-4045) This invention. relates to new carboxylic acid amido-alkyl-amino ester salts and to a process for the production thereof.

It is the prinicipal object of this invention to v properties as textile auxiliaries.

, It is a special object of this invention to produce surface active amine-amides containing as the amine radical quaternary ammonium alka-l mine esters.

"with this invention constitute a special class of Ra no onabonicnaii ynioo 0.11.

wherein R is a saturated or unsaturated cyclic or acyclic hydrocarbon, preferably an aliphatic or aralkyl, radical containing 8 to carbon atoms; R1 is H ora substituted or unsubstituted hydrocarbon radical, preferably an alkyl or aralkyl radical; R2 is H or a substituted or unsubstiand unsubstituted hydrocarbon radicals, preferably alkyl or hydroxyalkyl radicals; R4 is an aliphatic hydrocarbon radical, preferably an alkylene radical; Re is a hydrocarbon radical, preferably an alkyl radical of 11 to 17 carbon atoms; and Xis a halogen other than fluorine or other anion.

The novel carboxylic acid amido-alkyl-amine ester salts of this invention are produced by condensing an amide of an organic carboxylic acid containing from 9 to 21 carbon atoms in its acyl radical and containing a s-hydroxy aliphatic substituent on its amide nitrogen atom with a phosphorus halide (other than fluoride) or a tuted hydrocarbon radical, preferably an alkyl or aryl radical; R3 and R5 are the same or different radicals andrepresent H or substituted sulphur oxyhalide (other than fluoride) and with an alkamine ester of a carboxylic acid containing from 12 to 18 carbon atomsin the acyl radical.

The condensations and reactions of this invention take place readily under relatively mild heating and without the necessity for using pressure vessels. Normally temperatures below 140 C. are adequate and most condensations take place readily at 130 C. or below, as at temperatures of to C.

The amides used in the condensation reactions of this reaction maybe prepared-by known methods, such as that disclosed in British Patent 631,387, or by the reaction of carboxylic acids with appropriate primary or secondary amines, or by the reaction of amides with appropriate alkylene oxides, such as ethylene oxide or isopropylene oxide and the like. The acids from which the amines are derived may be known cyclic or acyclic high molecular weight carboxylic acids having sufficiently large hydrophobic molecular components to product the desired surface activity and the proper balance between hydrophobic and hydrophilic properties. Such acids preferably include aliphatic or aromatic aliphatic carboxylic acids containing from 9 to 21. carbon atoms. Especially valuable products are derived from high molecular weight fatty acids.

When the amide component is derived by reaction of a carboxylic acid with an amine, it may be derived fromknown ,B-hydroxy aliphatic primary or secondary amines. Suitable primary amines readily available commercially include monoethanol amine, monopropanol amine, monobutanol amine and b-hydroxy, mphenyl ethyl amine, such as derived from styrene. Presently commercially available fl-hydroxy aliphatic secondary amines include f such compounds ,as methyl ethanol amine, ethyl ethanol amine, diethanol amine and mixed aliphatic aromatic amines, such as benzyl ethanol amine.

The halogenated amine radical of this invention may be derived from known primary, secondary or tertiary alkamine esters. For example, secondary amine halides are derived from primary alkamine esters, tertiary amine halides from secondary alkamine esters and quaternary ammonium halides from tertiary alkamine esters. These alkamine esters may be obtained by known procedures, such as by reacting carboxylic acids with an appropriate alkanol amine.

'12 to 18 carbon atoms.

secondary or tertiary amine salts are desired as a the final product, appropriate primary or secondary alkanol amines or appropriate mixed alkyl alkanol amines may be used in producing the alkamine esters. For example, suitable amines for condensing with the fatty acids to form primary or secondary alkamine ester reactants include such compounds as mono-ethanol amine, monopropanol amine, mono-butanol amine, diethanol amine, methyl ethanol amine, ethyl ethanol amine, and the like.

Generally speaking, the compounds of the present invention can be obtained by condensing compounds having the formula:

RCO.NR1.CH2.CHR2.OH

with a phosphorus halide other than a fluoride or a sulphur oxy-halide other than a fluoride, and with an alkamine ester of a fatty acid of the general formula:

wherein the letters have the significance specified hereinbefore.

Thus a new class of amide-amine salts are provided wherein the amide component is an alkyl amide of a carboxylic acid containing from 9 to 21 carbon atoms in its acyl radical, and the amino component is an alkamine ester halide, other than a fluoride, substituted on the B-carbon atom of the alkyl radical and wherein the ester radical is that of a carboxylic acid containing Particularly valuable compounds are formed when the amideand the ester-forming acid radicals are derived from fatty I acids.

A preferred class of compounds produced in accordance with the procedures of this invention have the formula:

wherein R. is a saturated or unsaturated cyclic or acyclic hydrocarbon radical and preferably an alkyl or aralkyl radical of 8 to 20 carbon atoms; R1 is H or an alkyl or aralkyl radical which may be substituted or unsubstituted; R2 is H or an aryl radical which may be substituted or unsubide may be replaced by other salt-forming radicals, such as other anions.

The high yields and purity of the products of the process of this invention have been determined by surface active titration as disclosed by T. Barr et al. in their article The determination of surface active agents in solution, in Society of Chemical Industry Journal, vol. 67, February,

1948, pp. 45-48. The technique has been modimay be necessary to ascertain the appropriate weight of substance to be used. Ten mls. of this solution was transferred by pipette to a 50 ml. stoppered bottle and 1 ml. of N/2HCl, 20 mls. of CHsCl and 4 drops of methylene blue solution were added. The solution was then titrated with an M/ 1000 sodium dodecyl sulfate solution under vigorous shaking until the aqueous layer was completely colorless. The approach of the complete disappearance ofeolor was indicated by the rapidity of the separation of the two layers after shaking. At the completion of the titration both layers separated bright and clear. The titration was sensitive to about 0.2 ml. in an M/ 1000 solution.

Complementary discussions of surface active titrations will be found in the following articles.

Association of Official-Agricultural Chemists Journal, vol. 28, 1945. General colorimetric method for determination of small quantities of sulfonated or sulfated surface active compounds, by J. H. Jones, pp. 398-409.

Industrial and Engineering Chemistry (Analytical Edition), vol. 15, 1943 (July-December). "Germicidal quaternary ammonium salts in dilute solution, by M. E. Auerbach, pp. 492-493.

Industrial and Engineering Chemistry (Analytical Edition), vol. 16, 1944 (July-December). Colorimetric assay of quaternary ammonium salts, by M. E. Auerbach, p. 739.

Royal Society of London Proceedings, vol. 168, Series A (Mathematical and Physical Sciences), November 7, 1938. Determination of the paraffin-chain radical, by G. S. Hartley and D. F. Runnicles, pp. 424-425.

The Journal of the Society of Dyers and Colourists, vol. 61, July 1945. Tensimetric analysis of surface-active electrolytes, by J. M. Preston, pp. -166.

The following examples further illustrate the process and products of the present invention- Example 1 One molecular proportion of ,B-chlorethyl oleoyl amide is prepared by treating one molecular proportion of p-hydroxy ethyl oleoyl amide with one third of a molecular proportion of phosphorus trichloride while keeping the temperature of the reaction mixture between 60 and 70 C. by gentle cooling. One hundred forty-nine grams of triethanol amine is carefully added to a benzene solution containing 284 grams of stearic acid and the benzene solution is heated under reflux under a water trap until 18 grams of water have been separated and the acid value of the reaction mass has fallen below five. The solution of the formed bis-(B-hydroxyethyl) amino-ethyl stearate is added to the separately prepared B-chlorethyl oleoyl amide and the mixture is refluxed for four hours during which time the quaternary amide ester chloride is formed. Then the benzene is removed by distillation and the reaction product is isolated as a pasty solid. This material readily emulsifies in water and can be used in the form of an aqueous paste as a textile auxiliary.

1 Thereafter the mulazi.

. 1S. .QH2VCH2.;

oleoylgradical, By substituting phosphorus tribromide or phosegtaavoa ey substituting phosphorus tribromide or phosphorus triiodide in the reactions of this invention jthe. corresponding bromide and iodide salts are obtained. 1 v yfimampleZf r Asolution'of one. molecular proportion or N-flhydroxyethyl N-methyl aminoethyl oleate is pre- 'pared; by gradually introducing 119 grams of N- .{methyl .diethanol- .amineminto. a solution. of. 282 grams of oleic acid in 500 grams. of toluene and a then gradually refluxing: the mixture until .18 grams. of water hayeformed and have been-re- .mOVEd fromthe-reaction; proportion of .N-p-c hlorethyl N-benzyl. oleoyl amide is formed byreacting-one molecularproportion. of. N -fl-hydroxy-ethyk l lil-benzyl oleoyl amide with. /3 Of a. molecular proportion of phos-- phorustrichlorude; In order to produce the reaction product, the: phosphorus trichloride is .addedto theoleoyl amide While. maintaining the reaction mixtureat 6.0 to 10 C' by external coolru ingaandthen thereaction is completed: by stirring the mixture :for an, The formed oleoyl.;.amide additional half hour. and. alkamine. oleate are then: mixed andrefiuxed. foraf our hours in .ordento form the; desired amine-amide salt.

gunder a partial; vacuum leaving a buttery mass which readily .dispersesin; water and has superior properties as La .textile. finishing and anti- .static agent. i

procedure previously de- The reaction product has the following for- CmdaHafl om r a a canto ou -om. CBztN-CHL Q32. o o o uru;

01 CHzCHzOH ancewiththis example,- the symbols in the repre-r phorus triiodide in the reaction of this invention the corresponding bromide and obtained.

Example 3 responding molal quantity of bis-(fi-hydroxyethyl) amino ethyl oleate is prepared as described hereinbefore or as described in British specificasolvent: is removed by evaporation; i

iodide salts are i .erally useful: as capillary active textile treating .agentsJ They are. auxiliaries for inhibiting. the formation of. elecmula:

a member of the group consisting of H, hydroxyalkyl radicals; R4] represents an alkylene Ia t'ion 587L534. 'l-heiormed amide and alltamine j ester are mixedgjand heated at C: I for four which readily disperses in water and finds wide applicability as. a textile auxiliary The reactionfproduct has the following forl .1 C1 YGHZCHZQH i Thus, in accordance with this example; the symin therepresentative formula have the foleach .CH2.CH20H; R4 is .CH2.CH2.; .OORt i's the oleoyl radical, C17H33CO.;.and-X is Cl.

By substituting thionyl tribrornide or thionyl triiodide in the reactions of this: invention the corresponding bromide and iodide salts are obtained. 3 =1: w I The new compoundsiof this invention are genespecially useful as. textile cellulose acetate textile materials.

The practice ofthis invention has been exemplified in the specification by various details and examples: "It willyxbe rmderstood, however, that the appended claims. l i

What isuclaimed is: U

ss of compounds of the general wherein R representsa member of the group consisting of cyclic and acyclic hydrocarbon radituted and unsubstituted alkyl and aralkyl radicals; R2 represents a. member of the group consisting of'I-Lan alkyl radical, and substituted and unsubstituted aryl radicals;

" cal; Ra. represents saturated and unsaturated hatiohydrocarbon radicals of I1. to '17 carbon gen atom other than fluorine. 2. A new class of compounds of the general formula:

/Ra R.CO-NH-CHLCHRz-IFqRgO-O0.-R6

wherein R.CO. represents a fatty acid acyl radical of 9 to 21 carbon atoms; R2 represents a member of the group consisting of H, an alkyl radical, and substituted and unsubstituted aryl radicals; R3 and R5 represent a member of the group consisting of H, alkyl and hydroxyalkyl 7 radicals; R4 represents an alkylene radical;-'CO.Rs represents afatty acid acylradical. of 12 to 18 carbon atomspandX is a halogen atom other 1 than vfluorine.

3. A new class of compounds of the general-1 formula: V r

- R: nooawacn omr mob0.1a

00.3.6 represents a fatty acid acyl radical of 12 a to 18carbon atoms; and X is a halogen atom other than fluorine. I A. A new class of compounds of the general 1 wherein R..C0. represents a fatty acid acyl radical of 9 to 21carbon atoms; R3 represents an alkyl radical; R4 represents an alkylene radical; R5 represents a hydroxyalkyl radical; 00.1% represents a fatty acid acyl radical of 12 to 18 carbon atoms; and X is a halogen atom other than fluorine- I v 5. A new class of compounds of the general formula: I C E[V3 Rs Itoor ronaomN moooaa wherein R.CO. represents a fatty acid acyl radical of 9 to 21 carbon atoms; R3 and R5 represent hydroxyalkyl radicals; R4 represents an alkylene radical; CORE represents a fatty acid acyl radical of 12m 18 carbon atoms; and X is a halogen atom other than fluorine.

6. Anew compound of the formula:

I 9. A process for producing carboxylic acid amido-alkyl-amino ester salts which comprises condensing an amide of a fatty acid containing .from 9 to 21 carbon atoms in its .acyl radical and 1 containing a ,B-hydroxy aliphatic substituent on its nitrogen atom with a compound selected from the group consisting of phosphorus halides other than fluoride and sulphur oxy-halides other than fluoride and with an alkamine ester of a fatty acid containing from 12 to 18 carbon atoms in its 'carboxylic acid esterifying radical.

10. A [process for producing carboxylicacid amido-alkyl-amino ester saltswhich comprises condensing a fatty acid amide containing from 9 to 21 carbon atoms in the acyl radical and containing a p-hydroxyalkyl substituent on its nitrogen atom with a compound selected from the group consisting of-phosphorus halides other than fluoride and sulphur oxy-halides other than fluoride and with an alkamine ester of a fatty acid containing from 12 to 18 carbon atoms in its fatty acid radical, the condensation with said alkamine ester taking place at refluxing temperatures in excess of 100 C; I V

11. A process for producing carboxylic acid amido-alkyl-amino ester salts which comprises condensing an amide of a fatty acid containing from 9 to 21 carbon atoms in its acyl radicaland containing a fi-hydroxy aliphatic substituent on its nitrogen atom with a compound selected from the group consisting of phosphorus halides other than fluoride and sulphur oxy-halides other than fluoride and with a tertiary alkamine ester of a fatty acid containing from 12 to 18 carbon atoms in its carboxylic acid esterifying radical.

12. A process for producingbarboxylic acid amido-alkyl amino ester salts which com-prises condensing a fatty acid amide containing from 9 to 21 carbon atoms in the acyl radical and containing a p-hydroxyalkyl substituent on its nitrogen atom with a compound selected from the group consisting of phosphorus halides other than fluoride and sulphur oxy-halides other than fluoride and with a tertiary aliphatic alkamine ester of a fatty acid containing from 12 to 18 carbon atoms in its fatty acid radical.

13. A process for producing c'arboxylic acid amido-alkyl-amino ester salts which comprises condensing a fatty acid amide containingfrom 9 to 21 carbon atoms inthe acyl radical and containing a fi-hydroxyalkyl substituent on' its nitrogen atom with a compound selected from the group consisting of phosphorus halides other than fluoride and sulphur oxy-halides other than fluoride and with a dialkanol alkamine ester of a fatty acid containing from 12 to 18 carbon atoms in its fatty acid radical.

References Cited in the file of this patent UNITED STATES PATENTS Date Bock May 12, .1942 

1. A NEW CLASS OC COMPOUNDS OF THE GENERAL FORMULA:
 9. A PROCESS FOR PRODUCING CARBOXYLIC ACID AMIDO-ALKYL-AMINO ESTER SALTS WHICH COMPRISES CONDENSING AN AMIDE OF A FATTY ACID CONTAINING FROM 9 TO 21 CARBON ATOMS IN ITS ACYL RADICAL AND CONTAINING A B-HYDROXY ALIPHATIC SUBSTITUENT ON ITS NITROGEN ATOM WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF PHOSPHORUS HALIDES OTHER THAN FLUORIDE AND WITH AN ALKAMINE ESTER OF A FATTY ACID CONTAINING FROM 12 TO 18 CARBON ATOMS IN ITS CARBOXYLIC ACID ESTERIFYING RADICAL. 